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Effects of Sulfur Doping and Temperature on the Energy Bandgap of


ZnO Nanoparticles and Their Antibacterial Activities
Kenassa Wakgari Aga, Mulugeta Tesema Efa, and Tamene Tadesse Beyene*
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sı Supporting Information

ABSTRACT: Metal oxide nanoparticles (MO-NPs) are presently an area of intense scientific
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research, attributable to their wide variety of potential applications in biomedical, optical, and
electronic fields. MO-NPs such as zinc oxide nanoparticles (ZnO-NPs) and others have a very
high surface-area-to-volume ratio and are excellent catalysts. MO-NPs could also cause
unexpected effects in living cells because their sizes are similar to important biological
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molecules, or parts of them, or because they could pass through barriers that block the passage
of larger particles. However, undoped MO-NPs like ZnO-NPs are chemically pure, have a
higher optical bandgap energy, exhibit electron−hole recombination, lack visible light
absorption, and have poor antibacterial activities. To overcome these drawbacks and further
outspread the use of ZnO-NPs in nanomedicine, doping seems to represent a promising
solution. In this paper, the effects of temperature and sulfur doping concentration on the
bandgap energy of ZnO nanoparticles are investigated. Characterizations of the synthesized
ZnO-NPs using zinc acetate dihydrate as a precursor by a sol−gel method were done by using
X-ray diffraction, ultraviolet−visible spectroscopy, and Fourier transform infrared spectroscopy.
A comparative study was carried out to investigate the antibacterial activity of ZnO nanoparticles prepared at different temperatures
and different concentrations of sulfur-doped ZnO nanoparticles against Staphylococcus aureus bacteria. Experimental results showed
that the bandgap energy decreased from 3.34 to 3.27 eV and from 3.06 to 2.98 eV with increasing temperature and doping
concentration. The antibacterial activity of doped ZnO nanoparticles was also tested and was found to be much better than that of
bare ZnO nanoparticles.

1. INTRODUCTION of the individual curve for various annealing temperatures


Nanoparticle (NP) investigation is presently a field of intense through the hν on the x-axis.
scientific research, attributable to a wide diversity of latent MO-NPs are special classes of nanomaterials that have
applications, such as biomedical, optical, and electronic harvested huge interest in the fields of systematic research and
fields.1−3 More importantly, semiconducting metal oxide in many supplementary practical disciplines because of their
nanoparticles (MO-NPs) have been treated with great chemical and physical properties and numerous actual
consideration for their benefits such as fast and profound applications.8,13 Engineered MO-NPs are among the widest
detection, portability, biomedical applications in drug delivery used and manufactured nanomaterials.14−16 Among MO-NPs,
systems, high microbial action, and relatively low cost ZnO-NPs have drawn unlimited attention among scientific
compared to other conventional procedures.4−7 However, investigators for therapeutic and diagnostic applications, due to
their high-energy bandgap is hindering their potential their least toxicity, biodegradable nature, and low cost.14,17,18
applications.8 The bandgap energy of a semiconductor ZnO-NPs can securely be used as medicine, preservative in
designates the energy required to excite an electron from the food processing and packaging, and an antimicrobial mediator.
valence band (VB) to the conduction band (CB).9 The optical They effortlessly disseminate into the food material, execute
bandgap energy (Eg) and absorption coefficient (α) are linked the microbes, and prevent a human being from dropping ill.19
by the equation (Tauc method)10,11 (αhν)2 = hν − Eg. Here, Doping, which consists of the intentional incorporation of
hν is the acting photon energy. The variation of (αhν)2 with hν impurities into host lattices, is the most commonly used
is plotted for a metal oxide nanoparticle annealed at different
temperatures and different doping concentrations. In semi-
conductors, electrons could make a jump from the VB to the Received: February 1, 2022
CB but not with the same ease as they do in conductors, since Accepted: March 4, 2022
the gap between the VB and CB is larger in the case of
semiconductors.12 Spectrophotometric techniques are used to
find the energy bandgap in semiconductors. The energy
bandgap was assessed from the intercept of the linear portion
© XXXX The Authors. Published by
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method to tune nanomaterials’ optical and chemical proper- temperature. The next 10 g of sodium hydroxide was mixed
ties.20,21 Amusingly, ZnO-NPs are testified by several studies as with 10 mL of double distilled water at room temperature.
nontoxic to human cells and stable at very high temperatures, Both solutions were stirred with a constant stirring for 30 min
harmful to microorganisms, and having good biocompatibility with a magnetic stirrer. Any changes during the synthesis were
to human cells; these facets required their usage as recorded carefully. Following its good mixing, NaOH solution
antibacterial agents.22,23 However, undoped ZnO-NPs have a was poured into the solution containing Zn(CH3COO)2·2H2O
higher optical bandgap energy (3.37 eV) and poor photo- with stirring for 5 min. Then, a burette was loaded with
catalytic and antimicrobial activities. It is indispensable to alter sufficient amounts of ethanol (50 mL), and it was titrated
ZnO-NPs to employ a major percentage of sunlight and boost dropwise to the solution containing both NaOH solution and
the optical properties of ZnO-NPs. Certainly, this enhance- Zn(CH3COO)2·2H2O with vigorous stirring using a magnetic
ment is due to the limitation of the countable ZnO-NPs stirrer at room temperature. After the reaction, a gel-like
drawbacks such as the wide bandgap, electron−hole product was formed. The obtained mixture was filtered using
recombination, and lack of visible light absorption/limited Whatman filter paper and then dried and kept for further
use of sunlight as a natural source.24 There are no strong calcination at various temperatures (500, 600, 700, and 800
descriptions of the mechanisms of bandgap widening in °C). These steps enabled us to obtain the desired ZnO
nanostructured ZnO outside the presence of vacancies as nanoparticles.
suggested by some researchers.19 Improving the photocatalytic 2.2.1. Preparation of Sulfur-Doped ZnO-NPs. ZnO-NPs
and antibacterial action of metal oxide semiconductors by synthesized at 600 °C were selected for doping. The selected
lessening the optical bandgap to mark potential absorption in ZnO-NPs (1 g) in 10 mL of ethanol and 0.01, 0.02, 0.03, and
the visible region and to impede the recombination of 0.04 g of ZnS in 10 mL of distilled water were mixed and
photogenerated electron−hole pairs has become a burning stirred for 3 h at room temperature. Finally, the mixture (S/
issue among scientists in recent years.25 Doping of wide- ZnO) was filtered, washed with double distilled water until the
ranging bandgap metal oxides with diverse elements was pH of the removed water reaches 7 to check the purity of the
recommended to overcome these drawbacks and shift their product, air-dried overnight, and heat-dried at 300 °C for 1
antimicrobial and photocatalytic response to the visible light h.26,27 ZnO−ZnS heterostructures were obtained using the
region. This work focuses on reducing the bandgap energy of sol−gel synthesis method after ZnO-NPs were doped with
ZnO-NPs by varying synthesis temperatures and doping with ZnS. The procedures were summarized pictorially as indicated
sulfur and testing antibacterial activities against Staphylococcus in Figure 1.
aureus, which can cause severe infections, like bloodstream
infections, pneumonia, bone and joint infections, and
endocarditis (infection of the internal lining of the heart
cavities and heart valves).

2. MATERIALS AND METHODS


To investigate the consequence of synthesizing temperature
and sulfur doping on the bandgap energy of ZnO-NPs, ZnO-
NPs were prepared by a sol−gel technique at different
temperatures and mixed with different amounts of ZnS. The
sol−gel procedure involves the conversion of a solution system
of a liquid sol into a solid gel phase. The sol−gel technique is a
favorite for the advantages of its repeatability, controllability of
compositions, and simplicity in processing.
2.1. Chemicals and Instruments. Chemicals like
hydrated zinc acetate (Zn(CH3COO)2·2H2O) ≥ 98% (Loba
Chemie Pvt. Ltd), sodium hydroxide (NaOH) ≥ 98% (Blulux
Laboratories Ltd, 121005), ethanol (CH2COOH), and zinc
sulfide (ZnS) 98% (Chemicals UDYOG, 121001 (India)) and
distilled water were used in the research work. ZnS was used as
a sulfur source for doping.
Different materials/apparatus such as beakers, measuring
cylinders, magnetic stirrers, an electronic balance, a muffle
furnace, crystallizing dishes, burettes, funnels, filter paper, pH
meters, spoons, sample bottles, and a pipette were used. Figure 1. Schematic representations of the synthesis procedures of
Advanced analytical instruments such as an X-ray diffrac- ZnO nanoparticles by the sol−gel process and their antibacterial
tometer (Drywell XRD-7000, Cu Kα (λ = 1.54178 Å) activity.
radiation), UV−vis spectrometer (SPECORD 200 PLUS
223E1128F), and Fourier transform infrared (FTIR) spec- 2.2.2. Characterization. The synthesized precipitates of
trophotometer (Perkin Elmer Spectrum two, wavenumber undoped and doped ZnO nanoparticles were characterized by
range 8300−350 cm−1) were used for this research work. X-ray diffraction (XRD), UV−vis, and FTIR spectroscopic
2.2. Preparation of ZnO Nanoparticles. ZnO-NPs were techniques. A 0.2 M concentration of each sample was
synthesized by means of the sol−gel technique. For the prepared in ethanol for UV−vis, but XRD and FT-IR were
preparation of ZnO-NPs, 7 g of dihydrated zinc acetate was used for measurements of solid powders. The diffraction
dissolved in 50 mL of double distilled water at room measurements were conducted on a Drawell XRD-7000 using
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Cu Kα radiation over a 2θ in the range of 30−70°. Absorbance characterized employing Cu Kα radiation over a 2θ in the
measurements were conducted with a UV−visible spectropho- range of 30−70°. The XRD patterns of the produced products
tometer for the determination of bandgap energies. The FTIR are revealed in Figure 2a, which indicates the crystalline
analysis was also done to detect the various characteristic arrangement under the hexagonal structure (JCPDS card no.
functional groups associated with the synthesized nano- 01-080-0074) with leading peaks at 2θ = 31.87°, 34.36°, 36.2°,
particles. 47.5°, 56.53°, 62.75°, 66.35°, 67.85°, and 68.99°. These lines
were indexed correspondingly as (100), (002), (101), (102),
3. RESULTS AND DISCUSSION (110), (103), (112), and (201) and matched to the hexagonal
ZnO nanopowder was obtained successfully by the sol−gel phase of ZnO. Increasing the annealing temperature can
technique. The color of zinc oxide was changed from white to increase the reaction rate of decomposition of precursors due
yellow upon heating and returns to white on cooling in open to the bonds in precursors being broken by the heat energy at
air. The comprehensive hydrolysis of Zn(CH3COO)2 with the high temperatures.
support of NaOH in ethanol should result in the formation of a The particles have a high crystallinity at a high temperature,
ZnO colloid. Attributable to the heating, Zn(CH3COO)2 800 °C, which was clarified by a sharp peak and the highest
within the solution undertakes hydrolysis developing acetate intensity. It can be seen that the particles formed are ZnO
ions and zinc ions. The profusion of electrons in the oxygen nanoparticles and the crystallinity of the particles is amplified
creates the hydroxyl groups (−OH) of alcohol molecules to with the increased annealing temperature. This is caused by the
form bonds with the zinc ions. Zinc hydroxide acetate is a fact that the leading higher diffusion rate at a high temperature
midway (an intermediate) product of the hydrolysis reaction, resulted in the increased growth rate of ZnO crystals. The
formed in the presence of H2O and OH− ions. The progression of larger crystals from those of smaller size leads to
intermediate could be straightforwardly converted into ZnO a reduction in the number of smaller particles, while larger
at higher temperatures and through prolonged refluxing. particles continue to grow.18 This trend is possibly due to the
NaCH3COO is water-soluble and could therefore be separated evaporation of water molecules of the ZnO nanoparticles and
easily from the end product.28 At the time of drying, Zn(OH)2 the reorganization of the NPs. In this study, it was observed
is completely converted into ZnO. The total chemical reaction that there is a continuous increase in the particle size through
to form ZnO nanopowder is specified as follows: increasing the temperature. The growth in the particle size is
due to the smaller particles agglomerating or amalgamating
into larger particles, which is a result of solid-state diffusion (an
atomic migration from one point to another through the solid).
Figure 2b exhibits the XRD patterns of undoped and S-
doped ZnO-NPs; the precise peaks were located at (2θ) =
31.87°, 34.36°, 36.2°, 47.5°, 56.53°, 62.75°, 66.35°, 67.85°,
and 68.99°. The diffraction peaks of the S-doped ZnO-NPs are
likewise in good agreement with those of hexagonal ZnO
(JCPDS card no. 01-080-0074) and are almost identical to
those of pure ZnO, indicating that the sulfur atoms have been
doped in the ZnO crystal and no new peak has been formed
due to sulfur.
It was perceived that the amounts of dopants affect the
intensity of the diffraction peaks. A decrease in the intensity of
doping is due to a change in electron density. Overall, the
intensity of the diffraction peaks decreases greatly through the
increase of dopant concentration, indicating a relative loss of
crystallinity due to lattice alteration. When sulfur ions are
amalgamated into the periodic crystal lattice of ZnO, a tension
is induced into the system, following the alteration of the
lattice periodicity and the decrease in crystal symmetry.29
Here, it is significant that the crystallinity of ZnO-NPs retained
As a result of the huge electronegativity and size variation
after doping and peak intensities decreased, indicating
among S and O, sulfur doping is one of the best ways to
improved particle properties (Figure 2a,b).
modify the structural and optical properties of ZnO.22 Sulfur
For sulfur-doped ZnO-NPs, the structure was modeled by
integration in ZnO-NPs is anticipated to modify the host
the replacement of a segment of the O−2 by S−2. Thus, the
optical character, which induces an intragap state. Further-
more, S is able to syndicate either through the component ZnO-NPs appear to be significantly sulfur-doped. Zinc
elements of the host (zinc and oxygen) or per impurities oxysulfides, ZnO1−x Sx, are known to have a lower bandgap
present in the sample (e.g., hydrogen), generating several than ZnO due to the effect of band-bowing. If the sulfur
different intermediate segments, such as SO2, S2O, H2S, doping were to be limited to an outer shell of each ZnO-NP,
H2SO3, and ZnSO4, which directs to undesired structural the resulting intermediate-stage NPs would consist of a
imperfections.27 shrunken ZnO core surrounded by a ZnS shell.29
ZnO nanoparticles were synthesized from precursor Zn- The crystallite sizes of both pure and S-doped ZnO-NPs
(CH3COO)2·2H2O by the conventional sol−gel process. The have been achieved from the full-width at half-maximum
obtained products were calcined at temperatures of 500, 600, (FWHM) of the supreme strong peaks of the corresponding
0.9λ
700, and 800 °C for 3 h, and then, the products were crystals using the Scherrer equation, D = β cos θ , where λ is the
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Figure 2. XRD patterns of ZnO-NPs (a) synthesized at different temperatures and (b) synthesized at varying dopant concentrations compared
with undoped ZnO-NPs.

X-ray wavelength, D is the average crystallite size, θ is Bragg’s


diffraction angle, and β is the FWHM in radians. The crystallite
size calculated based on the XRD result (by using the Debye−
Scherrer equation) was increased with the increasing intensity
due to the temperature and decreased with the decreasing peak
intensity due to the doping concentration (Table 1). The most
noticeable tendency versus particle size is that the surface-to-
volume ratio increases for smaller particles.29,30

Table 1. Calculated Crystalline Size of Synthesized ZnO-


NPs at Different Synthetic Temperatures and Doping
Concentrations
synthesis β D
S/N condition θ cos θ λ (nm) (radian) (nm) Figure 3. Ultraviolet−visible spectra of ZnO-NPs produced at
1 ZnO at 500 °C 18.170 0.7778 0.154 0.066 1.63 different temperatures by the sol−gel method.
2 ZnO at 600 °C 18.170 0.7778 0.154 0.054 2.00
3 ZnO at 700 °C 18.170 0.7778 0.154 0.048 2.23
4 ZnO at 800 °C 18.170 0.7778 0.154 0.040 2.67
versus photon energy for ZnO at various annealing temper-
5 0.99% S/ZnO 18.170 0.7778 0.154 0.043 2.52
atures. The estimated Eg values for ZnO at 500, 600, 700, and
6 1.96% S/ZnO 18.170 0.7778 0.154 0.049 2.22
800 °C were 3.34, 3.3, 3.27, and 3.31 eV, respectively. The
7 2.91% S/ZnO 18.170 0.7778 0.154 0.053 2.05
respective data from which the graphs in Figure 4 were
8 3.85% S/ZnO 18.170 0.7778 0.154 0.066 1.63
sketched and the bandgaps were calculated are given in Tables
S1−S4. The reduction in Eg is achieved by increasing the
annealing temperature. As the temperature increases, the
The light absorption properties of ZnO-NPs synthesized at amplitude of atomic vibrations increases, bringing about a
different temperatures were obtained with a UV−vis larger interatomic spacing.3 We propose that the surprising
spectrophotometer in the wavelength range of 200−800 nm, difference in Eg results from the internal strain parameters
which provides a double beam; one of the beams passes established within the ZnO-NPs at higher temperatures, as the
through a reference cell for system calibration, whereas the particles become larger. The internal strains could be
second beam passes via the sample. Finally, the absorbance associated with the incidence of organic ligands chained to
spectrum of the sample versus the wavelengths was plotted. the growing NP surfaces resulting from the synthesis
The UV−vis absorption spectrum of the synthesized ZnO-NPs reaction.11
at 500, 600, 700, and 800 °C is presented in Figure 3, which The S doping into ZnO-NPs intensifies the surface-to-
displays that the ZnO-NPs indicate an absorption peak in the volume ratio, which significantly enhances the visible light
UV range at 378, 379, 381, and 379 nm, respectively. After the absorption. The absorbance in the stated wavelength range
annealing temperature is amplified, the absorption edge slightly starting from 200 to 800 nm is improved upon S doping.
shifted to higher wavelengths. This shift is due to the Figure 5 shows that the maximum optical absorption was
improvement of the crystallinity of the NPs. obtained for the largest dopant concentration (3.85%), while
The optical bandgap (Eg) was calculated using the Tauc the minimum optical absorption was obtained for undoped
method. Typically, Eg for the synthesized ZnO-NPs could be ZnO nanoparticles. Thus, the more the dopant quantity, the
obtained by plotting (αhν)2 versus hν, where α and hν are the greater the optical absorption obtained. As the wavelength of
absorption coefficient and the photon energy, respectively. incident light declined to the ultraviolet region, the absorbance
Values of log A, α, hν, and (αhν)2 were calculated to determine of S-doped ZnO-NPs amplified with a fundamental absorption
bandgap energies for entire samples and are given in the edge at around 379 nm of wavelength. The absorption of the
Supporting Information. Figure 4 displays plots of (αhν)2 sulfur-doped ZnO-NPs at 0% (undoped), 0.99, 1.96, 2.91, and
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Figure 4. Bandgap energies of ZnO nanoparticles synthesized at various temperatures (a) 500 °C, (b) 600 °C, (c) 700 °C, and (d) 800 °C
determined using the Tauc method.

The corresponding data from which the graphs in Figure 6


were sketched and the bandgaps for the doped ZnO-NPs were
calculated are given in Tables S5−S8.
Light transmittance properties were measured for two
randomly selected samples by FTIR (Perkin Elmer Spectrum
two) in the wavenumber range of 4000−400 cm−1. Figure 7
shows the IR spectra of ZnO-NPs synthesized at 600 °C and
0.99% (S/ZnO) samples in order to see their difference in
functional groups. The IR spectra prove that the zinc oxide
absorption band with a stretching mode of Zn−O is between
400 and 850 cm−1, which corresponds to the hexagonal ZnO
crystal structure.25 Peaks sandwiched between 2730 and 3050
cm−1 are due to the C−H stretching vibration of alkane
Figure 5. Ultraviolet−visible absorbance spectra of synthesized ZnO
groups. The peaks observed between 1720 and 1300 cm−1 are
nanoparticles doped with variable quantities of sulfur.
due to the asymmetrical and symmetrical stretching of the zinc
carboxylate, which comes from reactive carbon-containing
3.85% displays that the ZnO-NPs exhibit an absorption peak in plasma species during synthesis. These observations from the
the UV range at 319, 376, 376, 377, and 379 nm, respectively. FTIR bands indicated the existence of impurities mainly near
The redshift (bathochromic shift), shift to longer λ, of the ZnO surfaces. In addition, there is a strong absorption peak
optical absorption edge must be related to the bandgap observed at 900 cm−1 in both samples assigned to Zn−O. A
reduction led by the semiconductor−sulfur accompanied by new peak, which is not sharp, was observed at 1498 cm−1 due
the merging of the donor and conduction bands. The light to microstructure formation of the sample (Zn−S) during
absorbance spectra of ZnO-NPs demonstrate an improved doping.31 The broadband at 3500 cm−1 is assigned to the O−
visibility with higher doping levels (dopant percentage H stretching mode of the hydroxyl group. The peak at 1310
composition). Normally, the quality of ZnO-NPs improved cm−1 corresponds to a CH3 bending vibration.32,33 The
with the elevating dopant concentration. In a similar manner to hydroxyl group resulted from the hygroscopic nature of
the undoped one, the energy bandgaps of doped ZnO-NPs ZnO.23,32 ZnO-NPs appear to be significantly sulfur-doped.
were also calculated from the UV−vis absorbance spectral Zinc oxysulfides, ZnO1−xSx, are recognized to possess a lower
values (Figure 6 and Tables S5−S8). Accordingly, the bandgap than ZnO as a result of the effect of band-bowing.30
estimated optical bandgaps of doped ZnO-NPs for different A pure culture of S aureus was obtained from Mettu Karl
doping concentrations (0, 0.99, 1.96, 2.91, and 3.85%) were Referral Hospital and activated in the Biology Laboratory of
3.3, 3.06, 3.02, and 2.98 eV, respectively. The decrease in the Mettu University for antibacterial activity tests. In this study,
bandgap observed is ascribed to the combined effect of 0.1 g of ZnO-NPs of different doping concentrations and
synthesis temperature and sulfur doping (Figures 4 and 6). different synthesizing temperatures were prepared in 1000 μL
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Figure 6. Bandgap energies of doped ZnO nanoparticles: (a) undoped, (b) 0.99% S/ZnO, (c) 1.96% S/ZnO, (d) 2.91% S/ZnO, and (e) 3.85% %
S/ZnO.

The zone of inhibition test method was selected for the


antibacterial test. The advantages of this method are the test
simplicity that does not require any special equipment and the
easier cost for testing. Employing a sterile swab, a suspension
of the pure culture was spread uniformly over the face of a
sterile agar plate. Figure 8 shows the antibacterial agent

Figure 8. Zone of inhibition test for the antibacterial activity of ZnO.

Figure 7. FTIR bands of undoped and 0.99% S/ZnO-NP samples. applied; the agar plate was incubated for 24 h, at a temperature
suitable for the test of the microorganism. The antibacterial
of distilled water. Interaction among NPs and the cell wall is agent leached from the object into the agar and then exercised
adequate to cause toxicity. If it is precise, formerly sufficient a growth-inhibiting effect; at that point, a vibrant zone (the
amounts of MO-NPs are needed so that the bacterial cells are zone of inhibition) appeared about the test product. The zone
entirely enveloped and shielded from their environment of inhibition was measured after 24 h of incubation. The
withdrawing no chance for nutrition to be engaged to continue antibacterial activity of ZnO could be reliant on the presence
the life process. It is comprehensively recognized that ZnO- of standard visible light.18,31 The magnitude of the zone of
NPs are antibacterial agents and inhibit the growth of inhibition is habitually correlated with the level of antimicro-
microorganisms by pervading into the cell membrane.19 bial activity present in the sample or product; a larger zone of
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inhibition usually means that the antibacterial activity is more Calculated values of log A, absorption coefficient (α),
potent (Figure 8). photon energy (hν), and (αhν)2 for ZnO-NPs at
The antibacterial activity increased as the calcination temperatures of 500, 600, 700, and 600 °C (Tables
temperature increased and as a function of sulfur loading S1−S4) and sulfur-doped ZnO-NPs with 0.99% S/ZnO,
contents because of a reduction of the bandgap energy of ZnO- 1.96% S/ZnO, 2.91% S/ZnO, and 3.85% S/ZnO
NPs. This has a consistent explanation with the hypothesis that (Tables S5−S8) (PDF)
ZnO-NPs with a smaller bandgap energy have a superior
antibacterial activity against S. aureus. In ZnO-NPs, a
significant number of excitons exist, but due to their wider ■ AUTHOR INFORMATION
bandgap, only a few electron−hole pairs could be created at Corresponding Author
room temperature. This important effect determines the Tamene Tadesse Beyene − Department of Chemistry, College
antibacterial activity of NPs. Table 2 shows the ZnO-NP of Natural Sciences, Jimma University, Jimma 251, Ethiopia;
synthesis conditions, bandgap energies, crystallite sizes, and orcid.org/0000-0002-1096-5557;
diameters of inhibition zones. Phone: +251917822252; Email: tamene.tadesse@
ju.edu.et
Table 2. ZnO-NP Synthesis Conditions, Bandgap Energies,
Crystallite Sizes, and Diameters of Inhibition Zones Authors
Kenassa Wakgari Aga − Department of Chemical Engineering,
synthesis bandgap crystallite size inhibition zone
S/N condition energy (eV) (nm) (cm) College of Technology, Mettu University, Mettu 251, Ethiopia
Mulugeta Tesema Efa − Department of Chemistry, College of
1 ZnO at 500 °C 3.340 1.630 1.401
Natural Sciences, Dambi Dollo University, Jimma 251,
2 ZnO at 600 °C 3.300 2.002 1.600
Ethiopia
3 ZnO at 700 °C 3.220 2.230 2.100
4 ZnO at 800 °C 3.310 2.674 2.000 Complete contact information is available at:
5 0.99% S/ZnO 3.060 2.515 1.700 https://pubs.acs.org/10.1021/acsomega.2c00647
6 1.96% S/ZnO 3.050 2.216 2.100
7 2.91% S/ZnO 3.020 2.056 2.200 Author Contributions
8 3.85% S/ZnO 2.980 1.626 2.400 T.T.B. drew the scheme in Figure 1 and the graphical abstract,
and K.W.A. took and labeled pictures in Figure 7.
Notes
The authors declare no competing financial interest.
4. CONCLUSIONS
In the present work, the impact of varied sulfur doping ■ ACKNOWLEDGMENTS
concentrations and different synthesis temperatures on the The authors are highly grateful for the financial support from
optical bandgap energy and the additionally crystalline Mettu University, Mettu-Oromiya, Ethiopia.
structure of ZnO-NPs, grown by the sol−gel method, was
studied and discussed. The XRD results showed similar REFERENCES
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